Production of lower-boiling distillates from higher-boiling petroleum hydrocarbons



Patented septa 28, 1926.

UNITED STATES PATENT OFFICE.

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This invention relates to the production of lower. boiling distillates'from hi her boilpetroleum hydrocarbons,- an; it compn-sesthe 'proces's cfdistilling higher b011- l ui petroleum hydrocarbons'with the aid of a 'ydrousw aluminum chlorid by-charg a still withthe higher 'boiling petroleum hydrocarbolis. nd a relatively small amount of i anhydrous'ziiuminumchlorid, and distilling,

10. advantageouslynnder agitation .of the oil,

with immediate removal of vapors from the stilluntil at least 'fliflper cent of the charge is collected as-a dist' ate which upon assay distillation, showsan ainount distilling beltween 392 F. and 518- F. at least equal to he amount distilling below 392 F.

I have, discovered, a way of produci a fivaluabl'e distillate in large quantities with the use of a relatively small proportion of o aluminum chlorid without having to resort to'refluxing means during the distillation. In accordance with my invention I distil in such away as to produce a distillate of a 'al'characher. By using not substantlallyoverflper cent of aluminum chlorid and advantageously lessas low as 1 per cent-b weight on the 'hi her boiling oil charged 'tb thelstill and conducting a steady distillation without special means-for re- Q'; fluxingpl produce from a given charges large quantity of lower boiling hydrocar- Under the conditions mentioned,

there is substantially no loss of aluminumv chloridand any traces of hydrochloric acid 85 foi'med,.in event-moist oils are used, may be removed by scrubbin the vapors of the distillateas the leave't e'still. Of the distillate "rodu between and per cent is of t a nature of gasoline and kerosene 0 and from 25 to 50' per cent is of the nature of the original oilchar'ged to the still, difier; ing somewhat in being more refined. Upon redistillation of the distillate in the usual manner the residual higher boiling oil is used part of the charge for a succeeding aluminum chlorid distillation. It is particularly useful here due to the fact that it contains less sulphur and more saturated hydrocarbons than normal gas oil.

50 In one distillation operation which may be considered an embodiment of the present invention using a 1,000 barrel still, there was charged about 950 barrels of high boiling oil (in this instance, gas oil) which upon test cient warm oil to bring the total 'of the still was continued aid in five hours the temperature ofthe oil in thep as distillate.

Application filed April 25. 1825. Serial ll'o. 25.826.

distilled over a range between 406 -F. and F. A. 1,000 barrel still is one which will hold 1,000 barrels'of oil with suflicient vapor space. for distillation. This oil was heated to about 300 F. There'was then added 1.80 per cent byweight of aluminum chloridin admixture charge 11 to 1,000 barrels The contents of the still were then further heated. No special precautions for refluxing were-:reBalftd-to and the vapors-were ;reinovedfas,;fa st .-as i'c duced. Ina proximatelyltenhoilrs 'dlStlllate appea in the condenser. "The'firing the next still was 460 F., the temperature of the vapor in the still at about one or warm from the top was 445 F., and thetemperature at the highest point in the va r line was 391 F. From this time on t e temperature at the highest point in the vapor lineexceeded 391 F. l

The'distillation was stopped thirty hours after the distillate first appeared in the condenser,-or forty hours'after the still was fired. The total distillate was collected in one receiver and it comprised 89 per cent of the original charge, the remainder of the charge being accounted for by residual oil in the still and by gas and coke. Ordinarily sass I carry out the distillation to a point where a at least 75 per cent of the charge is collected An assay distillation of the distillate collected, as a result of the above process using 1.80 per cent by weight of aluminum chlorid, showed 22 per 'cent distilling up to 392 F. 35' per cent distilling between 392 F. an 518 F.. and about 43 per cent distilling above 518 F.

According to another embodiment of my invention, and by way of illustration, using the same amount of gas oil of the same character as above described, and carrying out the distillation in the same manner but usihg 3 per cent of aluminum chlorid by weight on the gas oil charged, there was obtained 83 per cent of total distillate. This distillate, upon assay distillation, showed 35.5 per cent distilling up to 392 F. 36.5

B er

and about 28 per cent distilling above cent distilling between 392 F. and 518 The processes performed in the we desrihed resulted in the production of a istillate which, upon' assa distillation, showed" throughout the major portion of the distillation the temperature at the highest point in the vapor line exceeded 391 F.- If there is any moisture in the oil as charged there will be a slight formation of hydrochloric acid bill; the vapors of the hydrochloric acid formed, as well as any traces of aluminum chlo'rid going over with the vapors can be eliminated by suitable scrubbing apparatus. The distillate is removed from the still as fast as formed. With the amounts of aluminum chlorid stated, the distillate formed during the first few hours of the run showed a pre on'derance of lower boiling oil in the dist ate and the run progressed and the temperature gradually rose there wasa pre ponderance of higher boiling oil in the distillate, but the amount of aluminum chlorid in the still at any given time was such that it was active in conversion; and did not tend to accompany the vaporsforward.

I ordinarily carryout't he distillation until there is about 5. to-lO per cent of residual oil left in the still. The distillate produced under these conditions re resents 85 per cent of the original charge, t e remainder being accounted for as gas and coke. But while these are so far as at present advised, the

best working conditions, I may sto the rocess at a point where 75 per cent total 'stillate 'iscollected. In any event the distillate should be of such a character that, upon assay distillation, the amount distillingup to. 892 F. will not exceed that amount distilling between 392 F. and 518 F.

When the distillation is completed to the desired oint, the residue in the still may be removed in the usual manner, the aluminum chlorid recovered in accordance with wellknown methods; or the aluminum chlorid residue may be removed and-the still prepared for a new run in accordance with the rocess described and claimed in my copendmg application, Serial Number 680,512, filed December 13, 1923.

I claim:

1. In the production of lower boiling oils from higher boiling oils with the aid of aluminum chlorid by distillation of oil in the presence of the chlorid, the process which comprises limiting the amount of aluminum assay distillation, not more than Le'o eae having a greater amount di' -.-.between 392 F. and 518 F. than below eee F.

3. In the distillation of higher petroleum hydrocarbons with the aide anhydrous aluminum chlorid, the process which comprises distilling the higher boiling hydrocarbons in.the presence of aluminum chlorid with removal of va rs of distillate as produced and conduct the distillation until the distillate produc will show, upon may distillation vat least as much distillin between 392 F. wins" F. as will distill ow,392 E. i

4. In the distillation-of"'higher. .poil.ing petroleum hydrocarbo'ps-with the aid of anydrous aluminumfiehlorid, the which comprises adding not substantially over 3 percent of aluminum chlorid, conducting the distillation with removal 'of vacm of distillate as produced until at. le st 5 per cent of the original charge is collected as distillate which. upon assa distillation 'will show at least as much disti ing between 392 F. and 518 F. as will distill below 392 F.

5. In the; production of lower boiling oils from higherf boiling. oils with the aid of aluminum chlorid by distillation of oil in the presencejo'f the chlorid, the process which comprises limiting the amount of aluminum chlorid used to produces. distillate ual to at least 75. per cent'of the original 0 arge, such distillate, upon assay distillation, showing at least as much distilling between 392 F. and 518 FL as distills below 392 F.

6. In the production of lower boiling oils from higher boiling oils with the aid of aluminum chlorid by distillation of oil in the resence of the chlorid, the process whic comprises limiting the amount of aluminum chlorid used to produce a distillate ual to at least 75 per cent of the original c urge, such distillate showing, upon cent distilling under 392 F.

In testimony whercof I have hereunto afiixccl my signature.

) ALMER MCDUFFIE MCAFEE.

per a 2 I i.eo;,cse

The processes pe" ormed in the we deresulted' in t e production of a istillate which, upon' assa distillation, showed" chlorid going over with the vapors can be eliminated by suitable scrubbing apparatus. The distillate is removed from the still as fast as formed. With the amounts of aluminum chlorid stated, the distillate formed during the first few hours of the run showed a preponderance of lower boiling oil in .the distillate and asthe run progressed and the tem erature .gra' lly rose there wasa prepon erance of higher boiling oil in the dis tillate, but the amount of aluminum chlorid in the still at any given time was such that it was active in conversion; and did not tend to accompany the vaporsforward.

I ordinarily carryout't he distillation until there is about 5. tol-O pelcent of residual oil left in the still. The distillate produced under these conditions re resents 85 per cent of the original charge, 1; e remainder being accountedfor as gas and coke. But while these are so far as at present advised, the

best working conditions, I may sto the 4 rocess at a point where 75 per cent 0 total distillate 'is collected. In any event the distillate should be of such a character that,

1 upon assay distillation, the amount distilling' upfto 392 F. will not exceed that amount distilling between 392 F. and 518 F.

When the distillation is completed to the desired oint, the residuein the still may be removed in the usual manner, the aluminum chlorid recovered in accordance with wellknown methods, or the aluminum chlorid residue may be removed andthe still prepared for a new run in accordance with the process described and claimed in my copendmg application, Serial Number 680,512, filed December 13, 1923.

I claim: I

1. In the production of lower boiling, 0115 from higher boiling oils witlrthe and of aluminum chlorid by distillation of oil in the presence of the chlorid, the process which comprises limiting the amount of aluminum chlorid used and heating'insuch a manner and at such a rate as to roduce a distillate,

which upon assay distil ation will show at least as much distillin below 392 F. and 518 F. as will distill be ow 892 F.

2. In the distillation of her boiling petroleum hydrocarbons with t e aid of anydrous aluminum chlorid, the process which comprises heating in such a manner and at such a. rate as to produce a distillate having a greater amount distilling'cbetween 392 .and 518 F. than below 392 F.

3. In the distillation of higher boili troleum hydrocarbons witlr the aidfo anhydrous alilminum chlorid, the process which comprises distilling the higher boiling hydrocarbons in.the presence of aluminum chlorid with removal of vapors of distillate as produced and conductm the distillation until the distillate produce will show, upon assay distillation (at least as much 'distillin as will distill low392 F.

4. In the distillationef. hi

ducting the distillation with removal of vaors o distillate as produced until at. least tfiper cent of the original charge is collected as distillate which. upon assa distillation "will show at least as much distilling between 392 F. and 518 F. as will distill below 392 F.

5. In the: production of lower boiling oils from higherf boiling. oils with the aid of aluminum chlorid by distillation of oil in the presencejo'f the chlorid, the process which comprises limiting the amount of aluminum chlorid used to produces distillate ual to atleast 75 per centlof the original 0 arge, such distillate, upon assay distillation, showing at' least as much distilling between 392 F. and 518 F. as distills below 392' F.

6. In the production of lower boilin oils from higher boiling oils with the aid of aluminum chlorid by distillation of oil in between 392 anders F,

the presence of the chlorid, the process cent distilling under 392 F.

In testimony whereof, I have hereunto aflixed my signature.

ALMER McDUFFIE McAFEE.

Certificate of Correctioni fi'n; ishereb certified that in Letters Patent No. 1,601,636 granted Se v e application of Almer McDufiie;McAfee, oflort .animprovement in The Production ofLower-Boilin 1&6, upon Boiling requiring correction as follows:'

a 2 read between; and that the said Letters Distillates from Higher:

Petroleum Hydrocarbons an error appears in the printed .s ification ,Pline 63? claim '1,.for the wor atent ould be read'with this correction therein that the same may conform to the record of the casein the Patent Ollice.

Signed and sealed this 26th day of October, A. D. 1926.

WLL A. KINNAN,. -Aatmg GQmmz'saioner ofPate'nta.

. assay distillation, not more than-35% per Arthur, for

Certificate of Gel-erection.

It is hereby certified that in Letters Patent No. 1,601,636, granted September 28, 1926, upon the application of Almer McDuffie McAfee, of Port Arthur, Texas, for an improvement in The Production of Lower-Boiling Distillates from Higher- Boiling Petroleum Hydrocarbons, an error appears in the printed s ,cification requiring correction as follows: Page 2 line 63, claim 1, for the wor below read bef/wcen; and that the said Letters Patent should be readwith this correction therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 26th day of October, A.-D. 1926.

[emu] W A. KINNAN,

Acting Gomxmissioner of Patents. 

